Beryllium, The Chemistry and Literature Of

T h e C h e m i s t r y a n d L i t e r a t u r e

o f B e r y l l i u m

BY

CHARLES LATHROP PARSONS, B. S.

PROFESSOR OF INORGANIC CHEMISTRY INNEW HAMPSHIRE COLLEGE

EASTON, PA.:THE CHEMICAL PUBUSHING CO.

LONDON, ENGLAND:WILLIAMS & NORGATE

14 HENRIETTA STREET, COVENT GARDEN, W. C.

PREFACE.

This book is written with the main object in view of savingpreliminary study and labor to future investigators of berylliumand to point out some of the peculiarities of this interesting ele-ment which are apt to lead the novitiate toward erroneous con-clusions. Especially is it desired to call attention to the fact thata large proportion of its accredited compounds are in reality butindefinite solid solutions. This condition of the literature ofberyllium is due to the abnormal extent to which its hydroxideis soluble in solutions of its normal salts, giving rise to solids ofalmost any degree of basicity or to solutions with decreasedosmotic effects. Accordingly, results of analysis, freezing points,etc., give little evidence of the true nature of its compounds, un-less accompanied by proved definiteness of composition, a prooftoo often omitted throughout the whole field of inorganic chem-istry, but nowhere more than in studying beryllium and its com-pounds.

More labor has been expended upon the bibliography than itslimited extent may seem to indicate. It is believed that it willbe found to contain references to all or nearly all the originalarticles on beryllium and that the references to abstracts will alsobe found fairly complete through 1902. Since 1902 the originalarticles and chief abstracts have alone been entered. It has beendeemed advisable to include a brief abstract, at times critical intone, of each article, but it is not claimed that these abstracts al-ways cover the full subject matter of the original, although nothingimportant is intentionally omitted.

The Journals examined are approximately the same as thoselisted in James Lewis Howe's unexcelled Bibliography of thePlatinum Metals and the plan followed is in general the sameas outlined by him. The abbreviations used are familiar to allchemists.

Grateful acknowledgments are due especially to the libraries

IV PREFACE

of the Massachusetts Institute of Technology, the Library ofHarvard University, the Boston Public Library and to the Libraryof the American Academy of Arts and Sciences. Also to theBoston Atheneum and to the libraries of Columbia University,N. Y., and the Surgeon General's Office and the Patent Office inWashington. The author also desires to express his thanks andappreciation of a grant allowed him by the American Asso-ciation for the Advancenient of Science toward expenses inourrrdin the preparation of the Bibliography.

CHARUvS L.Durham, N. II., Oct. i, i

TABTST OF CONTENTS.

PART I.Chapter I. Introduction I - I O

Discovery, name, history, occurrence, preparation fromberyl, detection, separation, determination.

Chapter I I . Metallic Beryllium 11-16Preparation, properties, valency, alloys.

Chapter III . Normal Compounds of Beryllium . . . . 17-44Discussion, fluoride, chloride, bromide, iodide, oxide,sulphide, selenicle, telluride, trinitrkle, phosphide, cyan-ide, carbide, borocarbide, silickle, hydroxide, chlorate,broxnate, iodate, aulphateB, sulphite, tkiosulphite, dithion-ate, sulphocyaiiate, selenate, selenite, tellurate, tellurite,chromite.chromatc, molytodate, nitrate,nitrite,phosphate,hypophosphate, p/rophosphate, phosphite, pyrophos-phite, vanadate, araenate, antirnonate, columbatc, carbon-ate, silicates, silicotungstate, fluosilicate, aluxninate, fer-rocjyaiiide, ferricyanide, xiitro prusside, beryllium ethyl,beryllium methyl, beryllium propyl, formate, acetate,propionate, acetylacctonate, oxalatcs, tartrates, succin-att% picrate, alpha-Ijromcamphor sulphonate, rhodizon-ate, kroconate, citmco^nate, fumarate, xnaleate.

Chapter IV. Acid Salts of Beryllium 45-46Discussion, mono acid phosphate, acid arsenate, acidftelenites, acid oxalate, acid molybdate.

Chapter V. Double Salts of Beryllium 47-60Discussion, double chlorides, fluorides, iodides, milphides,cyanides, sulphates, sulphites, nitrites, phosphates, car-fronaUs, oxalate.s, tartrates, raceniates, malatefi.

Chapter VI, Basic Compounds of Beryllium 61-71Discussion, basic acetate, basic formate, basic propionate,ba*ic isobutyrate, basic butyrate, basic isovalerate, in-definite basic solid phases, basic sulphates, basic oxalatesvbasic carbonates, miscellaneous basic solid phases.

PART II.Bibliography of Beryllium . 72-168Authors' Index - * 169Subject Index 172

P A R T I .

C H A P T E R I.

INTRODUCTION.Discovery.In 1797 L. N. Vauquelin undertook to prove the

chemical identity of the emerald and beryl, which had alreadybeen suspected by Haiiy, and in the course of his analyticalresearch, discovered that a portion of the precipitate which hadpreviously been supposed to be aluminium hydroxide, was thrownout of its solution in potassium hydroxide on boiling. He alsofound that this new hydroxide was soluble in ammonium car-bonate, formed no alum and was in many ways different fromaluminum. These observations led him to announce in a paperread before the Institute on Feb. 14, 1898 (1798; i ) , 1 the dis-covery of a new "earth."

Name.In his first articles on the subject (1798; I, 2 and 3) ,Vauquelin refers to the newly discovered oxide as* "la terre duBeril," which was translated into Germsui as- "Beryllerde," frotnwhich the name Beryllium took its rise. At the end of Vauque-lin's first article, the editors of the Annales de Chrimie suggestedthe name "ghicine" for the new oxide, and Vauquelin in hisfourth publication (1798; 4) adopts the suggestion prefacing itsuse with the remark "on a donne le nom de glucine." As earlyas 1799, Link (1799; 3) had objected to the use of this term astoo closely resembling "glycine," already in use, and indeed,Vauquelin, himself (1798; 3) seems to have accepted it withreluctance. In 1800 Klaproth (1800; 1) objected to its usebecause the salts of the yttrium earths were also sweet andEkeberg- (1802; 1) agrees with this idea. The name "Beryl-lium" itself was used when, in 1828, Wohler, (1828; 2) for thefirst time, separated the metal. For the sake of uniformity ingeneral usage which is overwhelmingly in favor of the name

1 References are to Bibliography, Part II.

2 CHEMISTRY OF BERYUJUM

derived from beryl, and as "glucine" grew into use in Frenchliterature without being proposed by the discoverer, much as"beryllerde" in Germany, and for the reasons set forth in 1904,11 and 1905, 2, it has been deemed advisable to adopt the name"Beryllium/' already in use by far the majority of chemists.

History.Following the discovery of the element, Vauquelinstudied and announced the properties of some of its chief com-pounds. In 1828 the metal itself was produced in a very impureform by both Wohler (1828; 2) and Bussy (1828; 3). Awdejew(1842; 2) added materially to the literature of the subject andmade the first determinations *of the atomic weight that have anyclaim to accuracy. Weeren (1854; 1) and Debray (1855; 1)also carried on extensive investigations of the metal, its atomicweight and chief compounds. Joy (1863; 1) undertook an ex-tended research on the preparation of its compounds from beryland published a fairly complete bibliography of the subject tohis day. Atterberg and Nilson and Pettersson in the years be-tween 1873 and 1885, made large additions to the chemistry ofberyllium, and during these years a long, earnest and interestingdiscussion, which had begun as early as Awdejew's time, wascarried on by Nilson and Pettersson, Humpidge, Reynolds, Hart-ley, Lothar Meyer, Brauner, and others regarding the valencyof beryllium and its place in the periodic system. The discus-sion has continued up to the present day, but was in realitysettled when Nilson and Pettersson (1884; 7, 8) determined thevapor density of the chloride, and Humpidge (1886; 1) showedthat at high temperatures the specific heat of beryllium ap-proached very closely to normal. Kriiss and Moraht (.1890; 4and 5) made a re-determination of the atomic weight in 1890, andbetween the years' 1895 and 1899, Lebeau published an importantseries of articles which are summed up by him (1899; 11) inone of the very best articles on beryllium and its compounds.Urbain and Lacombe (1901; 2) and Lacombe (1902; 3) dis-covered the remarkable basic salts of the acetic acid series andParsons re-determined the atomic weight by new methods (1904,-5 X95J 5) a n d studied many compounds, especially the so-calleabasic salts of some of the earlier writers (1904; 10, 1906; 1, 2,

INTRODUCTION 3

3, 4, 13, 1907; 3, 10, 11). Numerous other investigators as willbe seen from the bibliography, have also contributed to thechemistry of beryllium.

Occurrence.The chief form in which beryllium is found innature is the silicate, beryl, Be3Al2(SiO3)6, (BeO, 13.5 percent.) including its gem forms, emerald and aqua marine amifrom this mineral most of the beryllium investigators have de-rived their material. Beryllium compounds have also been de-rived from gadolinite, Be 2 F 3 (YO) 2 (SiOJ 2 , (BeO, 10 per cent.)and leucophane, Na(BeF)Ca(SiO3)2 , (BeO, 10.3 per cen t ) .Other important minerals containing this element are chryso-beryl, Be(AlO2)2 , (BeO, 19.2 per cent.) ; phenacite, Be2SiO4,(BeO, 45.5 per cent.) ; euclase, Be(AlOH)SiO4 , (BeO, 17.3 percent.) ;bertrandite,H2Be4Si2O9, (BeO,42.1 percent.) ;and eudidy-mite, HNaBeSi3O8, (BeO, 10.2 per cent.). Helvite, danalite,epididymate, crytolite, erdmanite, muromontite, alvite, foresitearrhmite, siphlite, trimerite and meliphanite, are rare and complexsilicates', while beryllonite, NaBePO4, (BeO, 19.7 per cent.) ;herderite, (CaF)BePO4 , (BeO, 15.4 per cent.) ; hambergite,Be2(OH)BO3 , (BeO, 53.3 per cent.), are interesting merely froma mineralagical standpoint as natural occurrence of the element.Beryllium has also been noted in some natural waters, in mon-azite sand, and in some aluminous schists. I t is quite probablethat it would have been found more frequently in rock analysisif some simple method of separating it from aluminum hadbeen earlier known.

Preparation from Beryl.Since beryl is not directly attacked byany acid, except, perhaps, by hydrofluoric when ground to a dust,it must first be fused with some flux or be heated in the electricfurnace to a temperature (Lebeau, 1895; 5) which volatilizessome of the silica and leaves a residue easily attacked by hydro-fluoric acid. For those having the facilities, this latter methodpresents many advantages. Among the fluxes which, can be suc-cessfully used are sodium and potassium carbonates, calcium flu-oride, potassium fluoride, calcium oxide, and sodium and potas-sium hydroxide. The fluorides possess the advantage in subse-quent treatment, in the comparative ease of removal of the large

4 CHEMISTRY OF BERYLLIUM

excess of silica, but for other reasons have been seldom used.Under average conditions the caustic alkalies, preferably potas-sium hydroxide, give the most satisfactory results.

Beryl is readily attacked by about its own weight of potassiumhydroxide at a comparatively low heat in a silver or nickel cru-cible, although a salamandar or carborundum crucible can beused. Clay, graphite or iron crucibles are not available as theyare immediately attacked. The fused mass should be broken up,just covered with water, strong sulphuric acid added until presentin slight excess and the now gelatinous mass heated and brokenup until fumes of sulphuric acid are given off and the whole hasthe appearance of a fine white powder. The residue is1 nexttreated with hot water when the sulphates of beryllium, alumi-num, iron and potassium pass into solution and on evaporationmost of the aluminum separates out as alum and can be removed.The mother liquors, containing all of the beryllium together withimpurities, should be oxidized by boiling with nitric acid to con-vert the iron into the ferric condition, neutralized with ammoniaand enough sodium bicarbonate crystals added to saturate the so-lution. The liquid should now be wanned and shaken frequent-ly during a period of twenty-four hours, when most of t h e beryl-lium will pass into solution almost perfectly free from aluminumand also from iron unless other salts are present, which is some-times the case. By again dissolving and re-treating the residueleft after filtration, practically all the beryllium will be found inthe bicarbonate solution. To this solution ammonium sulphideis added to remove any dissolved iron and the whole dilutedto five times its original volume. By blowing steam throughthis solution to the boiling point the beryllium will be precipitatedusually as a fine; granular basic carbonate easily filtered andwashed. The basic carbonate will be found to be quite pure (1906 ;2) save for some two per cent, of occluded sodium salt, but itsCO2 content and the ease of filtration will vary great-ly with the conditions of the hydrolysis and the length,of the heating process. The method employed by Pollok(1904; 1) possesses some advantages in that he uses sodium hy-droxide, dissolves in hydrochloric acid and after filtering off

INTRODUCTION 5

the main part of the silica, without evaporation, passes hydro-chloric acid gas through the nitrate, to the saturation point, where-by most of the aluminum is removed as the tetrahydrated chlo-ride together with the remainder of the silica, and in a form whichpermits of easy washing. The beryllium may then be recovered,after oxidation of the iron, by its solubility in boiling acid so-dium carbonate, in which the impurities ordinarily present areentirely insoluble, or it may be obtained in a less pure form by itssolubility in ammonium carbonate, which is the method up tothe present time almost universally employed.

The final separation by ammonium carbonate has the disadvan-tage that notable quantities of aluminum and iron also dissolveand the use, in large quantities, of a somewhat expensive reagent.It has the advantage of yielding the basic carbonate in a formwhich is easily washed from all impurities except ammonia.As is the case when acid sodium carbonate is used, solutiontakes place much more readily in the strongly saturated reagent,and the subsequent partial hydrolysis is greatly hastened by large-ly increasing the mass of the water present and is in both casespractically complete on diluting to a two per cent, solution andheating to the boiling point. Steam is much more preferablethan direct heating as the violent and almost explosive "bump-ing" which is unavoidable in the latter case is thereby entirelyprevented. Although not noted until very recently, (1906; 4)the basic carbonate produced in this manner contains about twoand one-half per cent, of ammonia which can be removed by longboiling in pure water, which also gradually removes the carbondioxide and leaves the beryllium in the form of the hydroxide,no more readily washed than if it had been precipitated as such.In practice a much better method is to heat the basic carbonatein contact with many times its weight of water, to momentaryboiling with steam, filter and repeat several times with freshwater. This method is much more productive of results thanwashing with hot water, and the carbon dioxide is for the mostpart retained. The comparatively small amount of iron that dis-solves in acid sodium or ammonium carbonate may be removedby adding ammonium sulphide, shaking and filtering off the fer-


rous sulphide with special precaution as to its oxidation duringthe filtration. The hydroxide or basic carbonate thus producedis the best form to use as a starting point in the production ofother beryllium compounds.

Special purification from all other metallic elements can bemost readily secured by conversion into the basic acetate and re-crystallization from hot glacial acetic acid (1906; 1) . On theother hand, the material prepared by the sodium bicarbonatemethod (1906; 2) is pure except for a small amount of sodiumwhich can not be washed out. This can be removed by re-solu-tion in acid and precipitation with ammonia.

Other methods for the removal of iron, aluminum, etc., willbe noted under analysis.

SEPARATION AND DETERMINATION.Except in the case of such pure salts as can be directly ig-

nited to the oxide, beryllium is precipitated as the hydroxide,by ammonia or ammonium sulphide, washed with water to whicha little ammonium acetate or nitrate has been added (1906 ;2) and ignited to the oxide. When alone, its determinationpresents.no difficulty except the great tendency of the hydroxideto pass through the filter in the colloidal state when washed withpure water. This is, however, entirely overcome by the use ofammonium acetate or nitrate as already noted.

Detection.Follow the customary procedure of qualitativeanalysis until the sulphides insoluble in HC1 have been removed.Concentrate the filtrate so obtained to 25 cubic centimeters andwhen cold add two grams solid N&jO ,^ boil and filter. Acidifythe filtrate with H N 0 8 and add ammonia in excess. If no p re -cipitate is obtained beryllium is absent. Wash any precipi-tate formed and add it together with two to three grams solidNaHCO3 to 20 cubic centimeters (10 per cent, solution) ofwater in a test-tube or casserole and bring rapidly to boiling.Boil for one-half minute only and filter to remove all aluminum.Dilute the filtrate with 10 volumes of water (one per cent, so-lution) and boil. Beryllium hydroxide containing a little car-bonate will precipitate if present. Other elements do not in-terfere.

INTRODUCTION 7

Separation.In minerals and in admixture with other ele-ments, the ordinary treatmentto separate aluminum and ironshould be followed and the beryllium will be found togetherwith these two elements in their final separation. It is quiteprobable that beryllium has been weighed and calculated as1 alu-minum in many mineral and rock analyses.

Many methods of separation of beryllium from iron and fromaluminum, have been followed, although most reported analysesdepend on the solubility of beryllium hydroxide in ammoniumcarbonate. Vauquelin (1798; 1) proposed the use of ammoniumcarbonate, but his first separation depended upon the solubilityof beryllium hydroxide in potassium hydroxide and its precipi-tation on boiling. Gmelin (1840; 1) and SchafTgotsch (1840;2) both used this same method, but it is very far from being ac-curate. Scheerer (1842; 3) first proposed the separation ofthe last traces of iron from the ammonium carbonate solutionby means of ammonium sulphide. Berthier (1843; 2 ) suggestedthe use of ammonium sulphite as a reagent, but the method wasshown to be valueless by Bottinger (1844; x ) - I n x85O, Ravot(1850; 1) proposed the ignition of the mixed oxides in a currentof hydrogen, whereby the iron was reduced to metal and couldbe dissolved out with dilute nitric acid, or its mass determined bythe loss in weight. Debray (1855; 1) developed a separationdependent upon the action of zinc on the mixed sulphates, pre-cipitating the aluminum as a basic sulphate, but the method wasnever claimed to be quantitative. Joy (1863; 1) made a com-parative study of all methods proposed to his time. Gibbs (1864;3) first suggests the use of sodium fluoride, to quantitativelyseparate aluminum from beryllium, and Pollok (1904; 1) showsthat the fluoride separation is exceedingly sharp. Cooke (1866;1) after reducing the iron in hydrogen, volatilizes1 it in a currentof hydrochloric acid gas. Havens and Way (1899; 5) accomplishedthe same result without previous reduction of the oxide. Ross-ler (1878; 9) succeeded in separating beryllium from smallamounts of aluminum by precipitating with ammonium phosphatein presence of citric acid. Vincent (1880; 2) uses dimethylamineto precipitate beryllium salts and finds that the aluminum com-

8 CHEMISTRY Ol

pound is soluble in excess of the reagent; iron acts like beryl-lium. Renz (1903; 4) confirms this, states the same to be trueof methyl, ethyl, and diethylamine and claims the results to bequantitatively accurate. Zimmermann (iHHj\ 5) return* to theold potassium hydroxide method without any special addition.Schleier (1892; 6), Atkinson and Smith ( 1895; 9) , and ihirgass(1896; y) separate iron quantitatively from beryllium by nitroio-beta-naphtfcioL JLebeau precipitates the iron in nitric acid solu-tion with ferrocyanide, the excess of ferroeyani*!e with coppernitrate and the copper an sulphide. Hart (i85; (l) removesthe major part of both iron ami aluminum !>y careful precipita-tion of the sulphates with sodium carbonate, the beryllium beingthe last to precipitate, owing to the great solubility of its ownhydroxide in its own sulphate. Havens ( 1897; 41 separatesberyllium from aluminum quantitatively by the insolubility faluminum chloride tetrahydrate in a mixture *f hydrochloric aridand ether, which has been saturated with hyriiig *li*solm.l in the c*i.r-bonatc of ammonium formed. ll-Jwr and Van Oonlt (1^14;4) dissolve basic berylliunt acetatt* in chlorofr-nii leaving ironand aluminum acetates behind, Myvts (^^14; 71 rinove*i ironclectrolytically from a slightly acid M'4uti*n of tin* ^?l|!i:iii%using a mercury cathode. l%ar*soiijt mvl Robiri>o i vf**\ 1 1 seji-arate basic beryllium acetate in a jitre su%u* itmn oilier arctai^ ,by mctans of its ready solubility in hot glacial act*tic acul amicomparative insolubility in the same reagent when r**14 |*ar*sons and Barnes (1906; 2) %\mw the gullibility f IrryS)sitni hy-droxide in a saturated solution of acir! %m\hnn carUonatf*. ;indthe insolubility of the hydroxitle fif iron and aluitiiutuu ui thesame reagent. Glassmann (uôG; 8) reili^rovers tin* Miljiliiffseparation of Berthier (1843; 2) , Hottingrr (1844; t ) anl J w(1863; I ) , and the fact that the method h M i% jîiiilccl mti byFriedheim ( igo^; **) M>ys, iiniy and Sji%ir (trî8; 2) giveaccurate methods for its separation and detection,

INTRODUCTION

Determination.In the opinion of the author, the by means of acid sodium carbonate offers the quickest, mostdirect and best method for estimating beryllium in admixturewith other elements. The method of Havens (1897; 4) isequally accurate if care is taken to fully saturate with hydro-chloric acid gas.

The first portion of the analysis will be the regular procedure,followed to obtain the hydroxides of iron and aluminum ifpresent and the beryllium will be found also as an hydroxide inthis precipitate. The mixed hydroxides of which less thanone gram should be present, are dissolved in as little as possiblehydrochloric acid, oxidized by a little nitric acicl, ammonia addedto nearly neutralize and evaporated to about 25 cubic centimeters.This solution is then heated to boiling and added with stirringto 75 cubic centimeters of hot (75) water, containing I2f to 15grams of the pure crystallized acid sodium carbonate. Thebeaker which contained the chloride is rinsed with a little hotwater and the whole brought immediately to boiling and heldthere far one-half minute. Care must be taken not to confusethe evolution of carbon dioxide with the actual boiling of theliquid, which must take place. Under these conditions the beryl-lium hydroxide passes into solution, and the aluminum and ferrichydroxides are precipitated carrying with them a small amountof beryllium.1 The liquid is allowed to cool and settle and isfiltered into a liter beaker and washed three times with a hot(75) solution of acid sodium carbonate containing 100 gramsto the liter. 'Hie precipitate is now redissolved in hydrochloricacid and treated as before, allowing the filtrates and washingsto run into the same beaker as first used. The filtrate is nowcarefully acidified with hydrochloric acid, the beaker beingcovered to prevent loss by spattering, is boiled to remove allcarbon dioxide and the beryllium precipitated as hydroxide byammonia, avoiding any large excess. The precipitate is allowedto settle, the supernatant liquid decanted through the filter andthe precipitate washed twice with hot water, redissolved in a lit-

1 Uranium may interfere as has been pointed out (1908; 2) but it is sel-

dom present with beryllium and may be easily detected by ferrocyanideand its separation presents no difficulty.

10 CHEMISTRY OF BERYMJtUM

tie hydrochloric acid and again precipitated with ammoniato remove sodium salts invariably occluded in the firstprecipitation. The precipitate is now washed with hot watercontaining two per cent, ammonium acetate or nitrate until thewashings give no chlorine reaction. The hydroxide is ignitedto the oxide in a platinum crucible without previous drying, aiulweighed.

C H A P T E R II.

METALLIC BERYLLIUM.

Preparation.^Beryllium was first prepared in the elementarystate by Wohler (1828; 2) and by Bussy (1828; 3) , acting in-dependently, by the action of potassium on the anhydrous chloride.Davy (1809; 1) had previously attempted to reduce the oxidewithout success and Stromeyer (1812; 1) claimed to have re-duced the oxide by a mixture of carbon, iron and linseed oil in1812. Wohler according to the records has priority over Bussyand deserves further credit in that he made a careful study ofhis product, which being very impure led him to announcesome properties since shown to be erroneous. Debray (1855; 1)substituted sodium for potassium and passed his chloride, inthe sublimed state, over the melted metal. Menier (1867; 1)exhibited a sample of metallic beryllium at the Paris Exposition,which he had prepared by the action of sodium upon a mixtureof beryllium chloride and the double fluorides of beryllium andpotassium in a crucible of pure aluminum. Reynolds (1876; 3)reduced the chloride by sodium, and Nilson and Pettersson(1878; 3 and 4) used the same method and succeeded in obtain-ing a metal of 87 per cent, purity by fusing under a salt coverin a crucible of iron tightly closed. Again (1880; 6 and 7) thesame authors succeeded in procuring a metal of 94 per cent, puritybut it was not until Humpklgc (1885; 1, 1886; 1) made hisfinal specific heat determinations in 1885, that a metal of ashigh a degree of purity as 99.2 per cent, was obtained. Wink-ler (1890; 3) claimed to have reduced the oxide by magnesiumand Goldsmith (1898; 14) by aluminum, but both chemists wereundoubtedly mistaken. Kriiss and Moraht (1890; 4 and 5) re-duced the double fluoride of beryllium and potassium withsodium, obtaining their metal in hexagonal plates. Pollok (1904;I and 9) again produced the metal by decomposition of thechloride with sodium, and states that he was unable to fuse to-

1 2 CHEMISTRY OF BERYLLIUM

gcthcr t h e d a r k g r a y powder formed for the reason that itprobably volat i l izes a t ordinary temperatures without passingthrough t h e l iquid condition.

It was left t o L e b e a u (1898; 3) to develop an apparently sim-ple and easy m e t h o d for producing the metal almost free fromadmixture, w h i c h h e did by electrolyzing the double fluoride ofberyllium a n d of potassium or of sodium in a nickel crucible. Itis true t h a t W a r r e n (1895; 10) had claimed to manufacture themetal by t h e electrolysis of the bromide which does not conductelectricity, a n d Borche r s (1895; 11) had proposed the prepara-tion by m e a n s of electrolyzing the chloride, mixed with an alkalichloride b u t apparen t ly without result. Lebeau proved that theImlides of bery l l ium did ljjot conduct electricity so he addedsodium fluoride to beryllium fluoride, melted the mass in a nickelcrucible w h i c h itself became the cathode, and using a carbonanode, passed a cur ren t from a dynamo yielding normally 20amperes a t 80 vol t s . Care was exercised to keep the heat butlittle a b o v e tne me l t ing point and metal was obtained in hex-agonal c rys ta l s .

S

BERYLLIUM 13

son, 1878; 3) but no determinations of the temperature havebeen made.

The specific heat at ordinary temperatures is abnormal as inthe case of boron, carbon and silicon, but Humpidge (1885; 1,1886; 1) has shown that between 4000 and 5000 it remainspractically constant at about 0.62. The matter was one of long-controversy and the low results obtained by Nilson and Petters-son (1878; 3) and others was the chief cause of the belief inthe trivalency of beryllium. According to Humpidge (1885;1 and 6, 1886; i)^ the relation between specific heat and tem-peratures can be expressed by the empirical formula:

K/ = 0.3756 + 0.00106 t -*-. 0.00000114 /*.According to Thalen (1869; 2) w^10 w a s ^ r s t t o study the

spectra of beryllium it is characterized by a line 4572.0 in theblue and 4488.5 in the indigo of about equal intensity. Lockyer(1878; 10) finds beryllium lines in the sun's spectra. Hartley(1883; 5) makes a careful study of the arc spectra of the chlo-ride and publishes a chart of the spectra of beryllium, whichbesides the two lines in the visible spectra noted above by Thalen,he finds the lines 3320.5, 3130.2, 2649.4, 2493.2, 2477.7 f which3130.2 is the strongest and most persistent. Rowland and Tat-nall (1895; 4) in their exhaustive study of the arc spectra ofthe elements, found the most prominent lines for beryllium be-tween 2100 and 4600 to be

2348.697 2650.414 3321.2182350.855 2651.042 3321.4862494-532 3130-556 4572.8692494.960 3131.200

These observations were made with a grating of 21 *4 feetradius and 20,000 lines to the inch on a photographic plate 19inches in length and are unsurpassed for accuracy. Formanek(1900; 3) finds that the chloride treated with Alkanna tincturepresents a strong orange red fluorescence and yields three ab-sorption bands. Soret (1878; 11) finds that solutions of thechloride give no absorption spectra and only a feeble bluishfluorescence. Crookes (1881; 4) found that beryllium oxide,in high vacuo, gave a beautiful blue phosphorescence, but

14 CHEMISTRY 01? BERYLLIUM

no spectral rays. Hartley (1901; 1) finds that the lines x 3130.3and 2478.1 are still visible in solutions of berylliuni salts whenthe concentration has fallen so low as 0.000001 per cent.

The atomic weight of berylliuni is very close to 9.1. The firstdetermination was made by Berzelius (1815; 1) early in the lastcentury and were little more than approximations. The cor-rected results of other investigators with the ratio determinedare as follows:

Mean o i'Awdejew (1842 ; 2) BeO : BaSO, 9MWeeren (1854 ; 1) BeO : BaSOl 927Debray (1855 ; 1) BeO : 4CO, 9-MKlatzo (1869 ; 1) BeO : BaSO 9. 8Nilson and Pettersson (1880 ; 6) BeSO^H/): Bt-O. 9. K*4Kriiss and Moraht (1890 ; 5) BeSOl.4lI2O : IJeO - 9.0$Parsons (I9O4; 5) lB*0

METALLIC BERYLLIUM 15

attack the metal with evolution of hydrogen. The gaseous hy-dracida attack it violently if passed over the heated metal.Strong nitric acid has little effect upon the metal but weaker.acid attacks it giving off nitric oxide. It is but little acted uponby cold water, but is slowly converted into the hydroxide byboiling water.

Beryllium acts upon methyl and ethyl iodides, (Cahours, i860;1) replacing the iodine and forming beryllium ethyl and beryl-lium methyl. It also replaces mercury in its analogous com-pound and in mercury propyl, (Cahours, 1873; 1, Lawroff, 1884;3 ) .

Wohler (1828 ;2) thoughthehad prepared the selenide, telluride,arsenide and phosphide by fusing with the respective elementsbut his observations1 have not been confirmed. Beryllium hasprobably never been obtained in combination with hydrogen.although Winkler, (1891; 3) thought he had produced a hydride.Beryllium unites directly with carbon, boron and silicon at theheat of the electric furnace (Lebeau, 1895; 2, 1898; 7, 1899; 11).It reduces SiCl4 when heated, (Rauter, 1892; 2) .

Valency.The valency of beryllium was long in doubt andgave rise to an animated discussion extending over many yearsand calling forth much research. The question was in realitysettled when Nilson and Pettersson, (1884; 7) and (1885; 3) ,against all their previous contentions, found the vapor densityof beryllium chloride to be entirely in accord with the divalencyof the metal. Their determinations were made between 490 and1520" C, and above 10000, their results are quite constant forthe formula BeCl2. The divalency was confirmed by Humpidgeby the specific heat at high temperatures and by the \iapor den-sity of both chloride and bromide, (1886; 1), by Coombes,(1894; 6) by the vapor density of the acetylacetonate, and byUrbain and Lacombe, (1901; 2) by the vapor density of thebasic acetate. Rotsenheim and Woge (1897; 4) also found theformula for the chloride to be BeCl2 by the rise of the boilingpoint of its solution in pyridine.

Alloys of Beryllium.Our knowledge of the alloys of beryl-lium is confined solely to the work of Lebeau (1897; 8, li

l6 CHEMISTRY OP UERVU.it-M

4, 1899; n ) and, although he produced alloys with themetals ancjdrs nfberyllium and the metal to be allovrd with in intinjatr jnixtur**of carbon to a very high temjH*rature in tin* ehrtrit* inrn^rv, orthey are prrMluewl sirnultanrouslv with the eltrtroktir pr**!u'..tion of hc*ryllhimf by substituting a graphite inr thf nirkrl rrncible arul fusing in this the metal to b

C H A P T E R I I I .

NORMAL COMPOUNDS OF BERYLLIUM.All normal compounds of beryllium which are soluble in water

are strongly acid in reaction to litmus, dissolve notable quanti-ties of their own hydroxide which increases in amount with theconcentration of the solution, set free carbon dioxidefrom carbonates and attack certain metals. In short, theyact in many respects like the acids themselves would act fromwhich they are derived. In spite of these facts they show lesshydrolysis, and consequent smaller concentration of hydrogenions, at least in the case of the chloride, nitrate and sulphate,(Leys, 1899; 10 and Brunner, 1900; 1) when treated by thewell-known method of sugar inversion, than the correspondingsalts of iron and aluminum. By the same method of determina-tion, the hydrogen ions are thrown back into the undissociatedcondition when but a small fraction of the beryllium hydroxidehas been dissolved which the normal salt is capable of holdingin solution, (Parsons, 1904; 10). The reasons for these phe-nomena are not at present understood. The sulphate has beenrecently studied with a view to a solution of this problem,(1907; 10) and it has been shown that the addition of berylliumhydroxide to a solution of the sulphate, raises the freezing pointand diminishes the conductivity; that no beryllium enters intothe formation of a complex anion and that while the hydroxidecan be partially removed by dialysis if dialyzed into pure water,there is little evidence of a colloid being present. It has beensuggested that we may have here a new instance of solution,wherein the solid, when once dissolved, acts as a true solventfor its own oxide or hydroxide, and there are some analogieswhich point strongly to this view, (1907; 11).

To this same cause, whatever it may be, is due the factthat no normal carbonate or nitrite is known, and that thechloride, bromide, iodide and nitrate lose their anioa so readilywhen in contact with water that they cam only be prepared with


special precaution against hydrolysis and solution of the hydrox-ide formed.

BERYLLIUM HALIDES.The halides of beryllium, with the exception of the

chloride, were little known until Lcbeau gave them mostcareful study. They are, excepting- the fluoride, only pre-pared pure in the absence of all water. liy careful evaporationof the fluoride in the presence of ammonium fluoride or in anatmosphere of hydrofluoric arid gas, it can apparently be keptfrom hydrolytic action, (Lebeau, 1899; 11) but this is not trueof any of the other halides. On evaporating their solutions inwater they lose more or less of the gaseous hydracids, theresidue becoming more and more basic and remaining solubleuntil a surprising degree of basicity is reached. This hydrolyticaction is comparatively small in the case of the fluoride, but ispractically complete in the case of the chloride, bromide ami io-dide. By careful manipulation residues of almost any degree ofbasicity can be obtained and these mixtures of base ami normalsalt have given rise to claims for numerous oxyfluoridcs andcxychloridcs for the existence of which there is no other evi-dence than the analysis of the variable residues obtained.

Beryllium Fluoride, BeFa. The first experiments on therelation of fluorine to beryllium were made by GayLussac and Thenard in 18 n (18 n ; 1). l a te r in1823, Berzelius (1823; 1) made the fluoride by din-solving the oxide in hydrofluoric acid and described the proper-ties of the solution so produced and the residue left on evapora-tion, the basic nature of which he recognized. Klatzo (1869;x) made a short study of the fluoride, but the pure salt wa* notproduced until Lebeau (1898; 8, 1899; 11) made it by heatingthe double fluoride of ammonium and beryllium, which had pre-viously been dried over phosphoric anhydride, in a current ofdry carbon dioxide and cooled in an atmosphere of the name gas.He also prepared it by the action of hydrofluoric acid gas onthe carbide.

Properties.According to Lebeau the pure fluoride k a glassy,transparent mass having a specific gravity of 2.01 at '15*. It

NORMAL COMPOUNDS OF BERYLLIUM 19

becomes fluid towards 8oo, passing through a viscous condition,b u t above 8oo it begins to volatilize, yielding white and verydeliquescent crystals. It dissolves in all proportions in water,is only slightly soluble in absolute alcohol, but dissolves read-i ly in 90 per cent, alcohol. By cooling an alcoholic solution to 2 3 , one obtains a white crystalline mass which, however, meltseasily on rise of temperature. It is also soluble in a mixture ofether and alcohol. The majority of metalloids are without actiono n the fluoride. It is insoluble in anhydrous hydrofluoric acida n d is not altered by it, rendering the existence of an acid saltquite improbable. It is readily attacked by sulphuric acid. Thealkali metals and magnesium reduce it, but the difficulty of fu-sion and hydroscopicity renders the preparation of pure metal dif-ficult. With potassium the reaction begins below 5000. Lith-ium and magnesium act at about 6500. Aluminum fuses with-ou t alteration.

Beryllium Chloride, BeCL.Although Vauquelin (1798; 5)obtained the chloride in solution, the pure salt wasno t made until Rose (1827; 1) prepared it in thesublimed anhydrous state by passing chlorine gas overa heated mixture of carbon and beryllium oxide. Wohler (1828;2), Awdejew (1842; 2) , Debray (1855; x)> Klatzo (1869; 1),Nilson and Pettersson (1880; 6, 7, and 8, 1885; 3) , Pollok (1904;12) and others used the same method of preparation. Nilsonand Pettersson (1885; 3) prepared the chloride in very pureform for the purpose of determining its vapor density by theaction of dry hydrochloric acid gas on the metal. Lebeau(1895; 2, 1899; 11) utilized the carbide which is readily attackedwhen heated by both chlorine and gaseous hydrochloric acid.IvOthar Meyer (1887; 1) obtained the chloride by passing car-bon tetrachloride vapor over heated beryllium oxide. Bourion(1907; 7) prepares the chloride by the action of a stream ofmixed Cl and S2C12 on the oxide at a red heat. No matterwhat method is used the materials must be absolutely dry if apure chloride is to be obtained. Awdejew (1842; 2) and Atter-berg (1873; 7) thought they had produced a hydrous chloride.BeCl2.4H2O, by evaporating" the chloride slowly over sulphuricacid, but Parsons (1904; 5) shows that the procedure recom-

2O CHEMISTRY OF BERYLLIUM

mended invariably yields basic mixtures of varying degrees ofhydration. Atterberg's results are easily explained when oneconsiders that his formula depended solely on an analysis forchlorine alone, and although Awdejew gives no details of hisanalytical results, it is probable he was led to his undoubtedlyerroneous conclusion in the same way.

Properties.-The anhydrous chloride is a white crystallinesolid having a melting point about 440 (Lebeaii, 1899; n .Pollok, 1904; 12). Carnalley (1879; 1, 1880; 1, 1884; 9, 1884;10) obtained much higher figures, but was certainly in error.The boiling point is about 5200 as shown by Nilson and Fetters-son and confirmed by Pollok (1904; 1). Its vapor density firstdetermined by Nilson and Pettcrsson (1884; 7, 1885; 3) between4900 and 15200, is in entire accord with the formula RcCls. Thiswas confirmed by Hnmpidge (1886; 1). Rosenheim and Woge(1897; 4) showed that the molecular weight as determined bythe raising of the boiling point of a solution of beryllium chlo-ride in pyricline, was in agreement with the same formula.Its molecular heat of solution is 44.5.K0 and its molecular heatof formation is 155K0 (Pollok, 1904; 9) . Its magnetic suscept-ibility was determined by Meyer (1899; 3) . The fused chloridedoes not conduct the electric current, (Lebeau) but its alcoholicsolution is a conductor (Pollok, 1904; 1).

Beryllium chloride dissolves in water with great avidity and,unless special precautions are taken, with loss of chlorine ashydrochloric acid. On evaporation the solution loses hydrochlo-ric acid more or less readily according to conditions, and theresidue left, which may be of almost any degree of basicity, hasbeen mistaken for an oxychloride by Atterberg (1873; 7, 1875;4 ) . With ether it forms the compound BeCl r2f(C 3H s ) 8O],(Atterberg, 1875; 4 ) . It also forms a white crystalline com-pound containing the chloride with both hydrochloric acid andether (Parsons, 1904; 5), the exact composition of which hasnot been determined.* It is also readily soluble in alcohol, andyields a crystalline compound with it, but is almost insoluble inbenzene, chloroform, carbon tetrachloride and sulphur dichlo-

* Since this went to press a letter from H. Steinmetz inform* me that thene rryaUlKare In reality BeClr4H9O. It 1H accordingly certain from the condition* that thi* com-pound was never made by Atterberg. Its indent* firat ion belongs to StHnmet* My in-correct observation was qualitative only and made In the course of another in v**tf gallon,

THK AVTHOU.

NORMAL COMPOUNDS OF BRYIJJUM 21

ride (Ubeau, 1899; 11). It combines with ammonia gas andwith phosphine. Lebeau (1899; n ) claims that it forms manycrystalline compounds with the organic bases, but Renz (1903;3) was only able to obtain the compound, BeCl2 .(C8H7N2)2+H2O, with quinoline. By experiments on the chloride and sul-phate, Hdber and Kieson (1898; 9) were able to show that theirtaste was due to the cation. The chloride forms many doublesalts (vidi, Double Salts). According to Brunner (1900; 1)and Leys (1899; 10), beryllium chloride solutions are less hydro-l>zed than those of aluminum and iron, although about two percent, of the molecules are so decomposed. Awdejew (1842; 2)and Nilson and Pettersson (1884; 7, 1885 >* 3) claim that the sub-limed chloride attacks glass, but Parsons (1904; 5) states thatthis is probably incorrect.

Beryllium Bromide.The bromide was first prepared byWohler (1828; 2) by the action of bromine vapor on the metaland also upon a mixture of carbon and beryllium oxide. Ber-themot (1831 ; 1) obtained it in solution by dissolving the oxidein hydroforomic acid. Humpidge (1883; 7) also prepared it byacting on a mixture of the oxide and carbon with dry bromine.Ix'beau (1899; 11) prepared it by the action of bromine andgaseous hydrobromic acid on the carbide.

Properties.The anhydrous bromide is obtained always bysublimation and in colorless white crystals1. Its vapor densitydetermined by Humpidge (1886; 1) is in accord with the for-mula i>eBr2. Its melting point was determined by Carnalleyand Williams (1K79; 1, 1880; 1, 1884; 9 and 10) but the valuesobtained were much too high, as shown by Lebeau (1899; 11),who states that it fuses at about 4900 and begins to sublime some-what below this temperature. The fused salt does not conductelectricity, although Warren (1895; 10) claimed to make themetal in some quantity by clectrolyzing it. For a knowledgeof its chemical properties we are indebted almost wholly toLebeau (1899; n ) who states that it acts much the same asthe chloride. It dissolves in water with avidity, losing hydro-bromic acid on evaporation. It is soluble in absolute alcohol

22 CHEMISTRY OF KKKVLMUM

and forms a crystalline compound therewith. It combines withammonia and with the organic bases.

Beryllium Iodide, Be!2.Wohler (1828; 2) and Dcbray (1855;1) prepared the iodide by the action of iodine uj>on the metal,but we are indebted almost solely to Lebeau (1898; f>, 1899; u ) ,who prepared it in some quantity by the action of gaseous hydri-odic acid, or a mixture of hydrogen and iodine vapor, on thecarbide at about ytxf, for a knowledge of its properties.

Properties.According to Lebeau (1899; n ) , beryllium io-dide, as obtained in the sublimed state, consists of colorlesscrystals, which are quickly decomjx>sed in moist air. Their spe-cific gravity at 150 is close to 4.20. They begin to sublime belowtheir melting point which is 51c/. The melted iodide boils be-tween 585"" and 595". It is insoluble in benzene, toluene* spiritsof turpentine, and but slightly soluble in carbon disulphide.'11 Hi slightest trace of water attacks it immediately, but it is notquite MI sensitive after fusion, probably because less sur-face is exposed. It can be distilled without alteration in dry hy-drogen, nitrogen or carbon dioxide. Its iodine is readily re-placed by chlorine or bromine. Fluorine forms fluorides of bothberyllium ami of iodine. Fluorine and chlorine l>oth attack ittv**n when colcl, giving off heat and light. Cyanogen acts uponit at about a red heat, producing a white material, less volatilethan the iodide, which with water gives a clear solution reactingfor cyanides. Heated in oxygen, it takes fire at about a red heatand the vapor itself will burn even in air. Heated with sulphurit yields a sulphide of beryllium, readily decomposed by water.The vapor of phosphorus also attacks it, probably forming apliosphidt* of beryllium. Sodium, jjotasstum and lithium re-duce it at about 350. Magnesium reduces it at about 450.Aluminum, silver, copper and mercury are without ac-tion below the temperature of the softening' of glass.Hydrogen sulphide acts upon it, but only at elevatedtetnjjerattire* and yields a white sulphide. It absorbs largeamount* of ammonia gas and forms compounds which melteasily and can be crystallized on cooling* It reacts with a largenumber of organic compounds. It is soluble in alcohol and pro-

NORMAL COMPOUNDS OF BERYLLIUM 2J

duces a crystalline compound therewith. It also combines withether. It differs from the iodide of aluminum in not reactingwith cold tetrachloride of carbon. It also does not act upon C>C14,Acetic anhydride and anhydrous chloral give energetic reactionswith beryllium iodide. Ammonium compounds and organicbases, especially aniline and pyridine, produce crystalline com-pounds with it.

BERYLLIUM OXIDE.Preparation.The oxide is prepared by heating the nitrate,

sulphate, oxalate, hydroxide, basic carbonate or other salt ofberyllium containing a volatile acid radical, and even the chlo-ride, bromide and iodide yield practically all of their metal asoxide when evaporated from solution and heated. By evaporat-ing to dryness a mixed solution of beryllium chloride'and ammo-nium chloride and heating in air, an oxide so light and featheryis produced that it is difficult to retain it in the containing ves-sel.

Properties.The oxide is a white powder as ordinarily pro-duced which can be volatilized and crystallized at high tempera-ture. According to Levi-Malvano (1905; 7) a blue oxide isobtained by igniting the hexahydrated sulphate (vidi sulphates).1in the electric furnace, (Lebeau, 1896; 6, 1899; 11) it can befused and even volatilized and yields a crystalline mass slightlyharder than corundum. The crystals are hexagonal (Lebeau,1899; 11). Mallard, (1887; 4) states that they are positive andunaxial and he measured parameters a : / i= i :i.63O5- He fur-ther states they are isomorphous with zinc oxide, and Ebelmen(1851; 1) states that they are isomorphous with aluminum ox-ide. The oxide is diamagnetic (Nilson and Pettersson, i8$o;9) and its magnetic susceptibility has been determined by Meyer(1899; 3) .

The specific gravity was first determined by Ekeberg (1802;1) as 2.967. Rose (1848; 2) found 3.021 to 3.09, claiming thelower figure was obtained by high heating. Ebelmen (1851; 1)reported 3.058; Nilson and Pettersson (1880; 9, 1880; 10) ob-

1 Repeated attempts by the author of this book to reproduce this oxide

or even the hexahydrated sulphate have met -with failure.


tained 3.016 and Grandeau (1886; 2) 3.18. Later results onvery pure material gave Kriiss and Moraht (1890; 7) 2.9644;JLebcau (1896; 6, 1899; 11) at o, 3.01-3.025 ; [Arsons (1904; 5)at 4W, 2.9640. According1 to Lebeau, fusing the oxide had verylittle effect on the specific gravity.

The specific heat of beryllium oxide is 0.247 between o andioo (Nikon and Pettersson, 1880; 9 and 10}. According toTanatar it is 0.2898 between 100-117".

Crystals of the oxide have been produced by melting in theelectric furnace (Lebeau, 1896; 0 ) , by fusing a mixture* of beryl-lium silicate and potassium carbonate (ICbelmen, 1851; 1), byfusing a mixture of sulphate of potassium and sulphate of beryl-lium (f)ebray, 1855; I ) , by fusing a mixture of sulphate of JH>-tassium and phosphate of beryllium (Grand/an, 188O; 21, bydissolving the oxide in fused beryllium leueite {Hautefeuilleand IVrrey, 1890; 9) and by fusing the sulphate with silicicacid (HautefeitiHe and fVrrey, 1890; 14).

HeryIlium oxide* is not reduced by hydrogen, magnesium, so-dium, jK>tassium or aluminum (Lebeau, i8


The gaseous hydracids have no action on the oxide, evenat high temperatures. Strong hydrochloric and nitric acids dis-solve the oxide slowly. Strong sulphuric acid attacks it readilyforming the anhydrous sulphate which dissolves only slowly ondilution with water as hydration progresses. Rose (1848; 3,1855 2 ) states that beryllium oxide partially decomposes solu-tions of NH4C1, but loses this property if heated. Atterberg(l&73'> 7) states that the oxide is not soluble in fused potassiumhydroxide. According to Ebelmen (1851; 1), it is readily solu-ble in potassium bisulphate.

Beryllium Sulphide.Wohler (1828; 2) supposed he had madea sulphide by heating the metal with sulphur, but Fremy (1853;1) states that it was the only sulphide he could not produce bypassing the vapor of carbon disulphide over the hot oxide. De-bray (1855; 1) and Nilson and Pettersson (1873; 3) s t a t e t n a tberyllium and sulphur do not combine when heated together.Berzelius (1826; 2) supposed he produced a double sulphide ofberyllium and tungsten, but his results lack confirmation. Lebeau(1899; 11) at last made the sulphide by heating the anhydrouschloride and iodide with sulphur or with hydrogen sulphide.Also by the action of sulphur vapor on the carbide at a hightemperature. The sulphide is a white solid, immediately decom-posed by water. No other details are given nor further studyof this compound been made.

Beryllium Selenide, Beryllium Telluride.Preparation claimedby Wohler (1828; 2) , but probably he was mistaken.

Beryllium Trinitride.Attempts to make the trinitride (Curtiusand Rissom, 1898; 12) by the action of a solution of berylliumsulphate on barium trinitride failed, as it immediately brokedown to beryllium hydroxide and hydronitric acid.

Beryllium Phosphide.Claimed by Wohler (1828; 2), by theaction of phosphorus on the metal, but unconfirmed by thismethod. Lebeau, however, (1899; n ) prepared a compound ofberyllium and phosphorus, which he did not analyze or describe,by means of the action of phosphorus vapor on anhydrous beryl-lium chloride and iodide.

26 CHKAJISTKY OF iii-KYU.IUM

Beryllium CyanideHy the action of cyanogen gas on beryl-lium iodide, Lcbeau (1898; 6, ifyw; n ) produced a cyanidecompound of beryllium which he neither studied nor analyzed.

Beryllium Carbide, PeaC\~The carbide of beryllium has beenproduce* 1 by Lebeau (1895; 2* 1H99; n ) by heating a mixture ofone part carbon ancl two parts beryllium oxide in an electricfurnace, using a current of

NORMAL COMPOUNDS OF BERYLLIUM 2J

attacks it only superficially at a red heat. Mineral acids and es-pecially nitric acid dissolve it rapidly.

Beryllium Silicide.Lebeau (1899; n ) also obtained a silicideof beryllium, but was unable to purify it sufficiently to deter-mine its properties or formula.

Beryllium Hydroxide, Be(OH)2.Beryllium hydroxide is awhite gelatinous mass physically indistinguishable from alu-minum hydroxide and resembling it very closely from a chem-ical standpoint. It is precipitated from solutions of berylliumsalts by ammonia, ammonium sulphide, caustic alkalies and ba-rium carbonate. It is also precipitated by methyl, dimethyl,ethyl, and diethyl amines (Vincent, 1880; 2, Renz, 1903; 4) .Soluble normal carbonates throw down a basic mass which con-,sists largely of the hydroxide together with some carbonate.The latter may, however, be almost entirely eliminated by boil-ing. It is readily attacked by solutions of acids. It dissolvesslowly in concentrated solutions of ammonium carbonate (Vau-quelin, 1798; 1, et al.) and sodium bicarbonate. It is imme-diately soluble in a saturated boiling solution of sodium bicar-bonate (Parsons and Barnes, 1906; 2) . It is, however, almostinsoluble in a dilute solution and a strong solution which has"dissolved the hydroxide, on dilution (two per cent, or lessNaHCO8) slowly hydrolyzes in the cold and throws out the!-basic carbonate or does so immediately on boiling. It is almostinsoluble in normal sodium carbonate. It is soluble in sodiumand potassium hydroxides forming beryllonates which are hy-drolytically decomposed on boiling. This decomposition is com-plete if excess of base is not present, but may be partially orentirely prevented by increasing the mass of the soluble hydrox-ide. It is soluble in solutions of its own salts and in proportionto the concentration of the particular salt used. From concen-trated solution in its own salts, it is precipitated by dilution,.but such precipitation is never complete. It is insoluble in ex-cess of ammonium sulphide, ammonia, and methyl, ethyl, di-methyl and diethyl amines (Vincent, 1880; 2, Renz, 1903; 4) .When washed with pure water it slowly passes through thefilter in colloidal solution (Parsons and Barnes, 1906; 2) . Beryl-

28 CHEMISTRY OP B&RYLUUM

lium hydroxide, like aluminum hydroxide, is more susceptibleto reaction when freshly precipitated (Haber and Van Oordt,1904; 2 ) . This is more especially apparent in the case of car-bon dioxide, for when freshly precipitated it will absorb aboutone third of an equivalent of this gas, but if allowed to standsometime and especially if first heated, it almost entirely losesthis property (Parsons and Roberts, 1906; 4 ) . Leys (1899; 10)states that it is 11 times as basic as aluminum hydroxide. Ithas, like most other gelatinous hydroxides, a very great tendencyto occlude other substances which may be present when it is pre-cipitated and it is almost imjx)ssil>le to remove these substancesby washing. It is nearly insoluble in water charged with car-bon dioxide (Sestini, 1891; 6) and according to Toczynski (1871;2) in hydrocyanic acid.

Van Benmielen (1882; 2) distinguishes two forms of the hy-droxide, first alpha, precipitated from potassium beryllonates byboiling which form is easily washed and, he claims, is the onlyone of definite composition being readily dried to the formulaBe(OH) 3 , and second beta, which is the gelatinous mass pre-cipitated by alkalies which is always more or less hydrated. At-terberg (1873; 7) gives formulas for some of these hydratedoxides, but there is little in his work or that of Van Bemmden({882; 2) to show that this extra water is other than mechani-cally held. ReubenbautT (1902; 5) found that sodium hydrox-ide dissolves beryllium hydroxide in proportion to its concentra-tion. Van Bcmmclen (1898; 19) studied the effects of heaton his two forms of the hydroxide. Meyer (1899; 3) deter-mined the magnetic susceptibility of the hydroxide. It is read-ily, although slowly, decomposed by boiling with solutions ofammonium salts (Rose, 1848; 3) , Debray (1855; i ) , Joy (1863;i ) , Parsons (1904; 5, et al.) v, Kobell (1832; 1) states thatcalcium carbonate will not precipitate beryllium hydroxide inthe cold, but does M> on boiling. Fnidhummer (1805; 7) statesthat beryllium hydroxide does not act as a mordant.

The heat of neutralization of beryllium hydroxide an foundby Thomsen (1871; i, 1874; 2) is

NORMAL COMPOUNDS Of B^RYI^ IUM 29

Be(OH) 2 +H s SO*4-Aq=i6 ioo calories.Be(OH) 2 - f2HCl+Aq=i3f i4o calories.

Pettcrsson (1890; 8) foundBe(OH) 2 - f2HF- f Aq=i9683 calories.

Gmelin (1840; 1), Schaffgotsch (1840; 2), Weeren (1854; 1),and Debray (1855; r ) have also studied the properties of beryl-lium hydroxide.

Beryllium Chlorate, Jfroma/te, Ioiate, and compounds of beryl-lium with oxyg-en and a halide.

Traube (1894; 3) gives the molecular solution volume ofBe(ClO3)2, but no details as to the salt itself. Atterberg- (1873;7) prepared the perchlorate, Be(ClO4)2.4H2O, and a periodateto which he gave a very improbable formula. He could notmake the chlorate. Marigiiac (1873; 2 ) tried to make the bro-rnate and iodate as well, but obtained only indefinite gummymasses. He states further that the perchlorate only takes thecrystalline form after concentration to a thick syrup and is verydeliquescent. Marignac was probably the nearest correct and itis doubtful if any of these compounds ha-ve been made as distinctindividuals.

Beryllium Sulplates.Six: normal sulphates of beryllium findplace in chemical literature:

BeSO,,BeSO4.H2O,BeSO4.2H2O,

BeSO4.6H2O,

of which the heptahydrate certainly has no existence, in fact..Anhydrous Beryllium Sulphate, BeSCVNilson and Petters-

son (1880; 9) prepared a product very close to the compositionBeSO4 by heating the dihydrate at 2500. The sulphate so prerpared had a specific gravrity=2.443 and a specific heat=o.i978.Lebcau (1896; 6, 1899; r i ) prepared the anhydrous sulphate bythe action of strong sulphuric acid on the oxide and evaporationof the excess of acid. Parsons (1904; 10) states that while


the product obtained by either of the foregoing" methods is un-doubtedly the anhydrous sulphate, it is a very difficult matterto get it pure, owing to the fact that the loss of the last traceof water on heating is very close to the point where sulphurtrioxide begins to be given off if indeed the two dc not go to-gether. Levi-Malvano (1905; 7) claims that this is a mistakeand that he completely eliminated all water at 2180 to 2200.

The anhydrous sulphate is stable in dry air, is itself insolublein water, but slowly hydrates and goes into solution as the tetra-hydrate. It loses sulphuric anhydride even below a red heat,but the last traces are only driven off at a full white heat.

Beryllium Sulphate Monohydrate, BeSO4.H2O.Levi-Malva-no (1905; 7) claims the dihydrate melts at 1580 and goes overinto the monohydrate.

Beryllium Sulphate Dihydrate, BeSO4.2H2O, is prepared bydrying the tetrahydrate at ioo and is stable in dry air belowthis temperature. Nilson and Pettersson (1880; 6) , Kriiss andMoraht (1890; 7) , Parsons (1904; 5, 1904; 10), Levi-Malvano(1905; 7). It dissolves readily in water passing back into thetetrahydrate.

Beryllium Sulphate Tetrahydrate, BeSO44H2O.The tetra-hydrate was first prepared by. Berzelius, (1815; 1) who con-sidered it to be an acid salt. Awdejew (1842; 2) first deter-mined its true character and used the salt to determine the atomicweight of beryllium. It was also employed for this purposeby Weeren (1854; 1), Klatzo (1869; l)> Nilson and Pettersson(1880; 6) and Kriiss and Moraht (1890; 7). Parsons (1904; 5)showed that the sulphate lost water continuously over phosphoricanhydride and discarded it as a means of determining the atomicweight of the element. This salt of beryllium has been studiedmore than any other compound of the metal.

Preparation.It is best prepared by dissolving beryllium ox-ide, carbonate or hydroxide in excess of sulphuric acid, evapo-rating in platinum and heating below a red heat until the largerpart, but not all, of the white fumes of sulphuric acid havebeen driven off, dissolving in water, evaporating to a syrup andturning into strong 95 per cent, alcohol. By this procedure a

NORMAL COMPOUNDS OF BRYIXIUM 31

milky solution is produced which does not immediately crystal-lize, but after a few hours the sulphate will have almost entirelyseparated. To insure perfect freedom from acid two morecrystallizations from alcohol are necessary and the salt shouldfinally be crystallized from water to insure the right degree ofhydration. The salt may also be prepared more directly andin a fair state of purity by evaporating the sulphuric acid solu-tion to dryness and heating on a sand bath until white fumescease to come off, taking especial care not to use too high a tem-perature. The anhydrous sulphate may then be allowed tostand for some time, with occasional stirring, in contact with coldwater filtered and the solution evaporated to crystallization.

Properties.Beryllium sulphate tetrahydrate consists of color-less octahedral crystals belonging to the tetragonal system. Ac-cording to Topsoe (1872; i ) and Topsoe and Christiansen (1873 ;9) the crystals are unaxial and optically negative. Observediorms ( o n ) . ( n o ) ; a:c=i : 0.9461. Mean indices of refraction

C = 1.4374 C = 1.4691c D = 1.4395 w D = 1.4720

F = 1.4450 P = 1-4779Wulff (1889; 4) states further that the crystals give strong*double refraction. Gladstone and Hibbert (1897; 6) comparedthe molecular refraction of the solid sulphate, 47.41 with thesame in solution, 47.94. Jahn (1891; 5) found the specificrotation for the sulphate as 0.28895. The solution friction wasstudied by Wagner (1890; 12). Meyer (1899; 3) studied themagnetic susceptibility. Traube (1894; 3) determined the molec-ular solution volume. Hober (1898; 9) found that the sul-phate and chloride have same sweet taste at equal cation con-centrations. According to Leys (1899; 10) and Brunner (1900;1) the sulphate is less hydrolyzed in solution than the sulphatesof aluminum and iron. Brunner gives this hydrolysis in N/4to N/20 solution as 0.52 per cent, to 0.68 per cent. Accordingto Weeren (1854; 1) the crystals lose one-third of their waterof crystallization at 350. Parsons (1904; 5) by tensimeter ex-periments found the vapor tension of the crystals at 200 to equala pressure of 20 millimeters of olive oil and to increase rapidly

$2 CHEMISTRY OF BERYLLIUM

with the temperature. Over phosphoric acid the crystals losewater slowly at ordinary temperatures. By dissolving one molHeS()4.4lIsC.) in 400 mols of water Thomsen (1H73: 4) foundthe heat of solution =-{-1100. Pollok (1904; 9) gives the heatof solution as 0.85K". The specific gravity has been deteiminedas follows: Topsoe (1872; 1) (1873; f>) 1.725; Xiiwm andi'ettersson (1880; 9) 1.713; Stalk> (Clark's "Constant* ofNature") 1.6743 at 22tJ; Kriiss and Moraht (1890; 7} 1.71^5.

Beryllium sulphate tetrahydrate is soluble in about its ownweight of water, but is insoluble in absolute alcohol. Its solu-tion is strongly acid to indicators, attacks zinc with evolutionof hydrogen and when fully concentrated dissolves two equiva-lents of its own hydroxide. On dilution the main portion ofthe hydroxide is thrown down, but approximately *>m*-half ofan equivalent remains dissolved at infinite dilution. It hmiklhe crystallized from a neutral or acid solution, for althoughthe crystals can be obtained from a basic solution (1906; 5) itis imjwsMbie to separate them therefrom. The taste of thesalt is a mixed acid and sweet.

Beryllium Sulphate Hexahydratt. - -Marignar {1873 ; 1 |, in at-tempting to repeat Klatxo's work (1869; 1) on the hepuihytirate,after many attempts obtained only once, Iiy evajiorating asaturated solution of srKlium sulphate and tieryllitiftt sua mans of prismatic crystals which he thought contained s\xmolecules of water. They imme%liately effloresced on exposureto air and could not have bvtn the hexahydrate drHcriiied byl^evi-Malvano (1905; 7) . According to the !a*t nantrf! authorhe otftaineil crystals of the hexahydrate frrttn a eotttmenrialsource and after repeated trials was able to produce the iwilt it-self by treating" an excess of but a little diluted sulphuric ackfwith enough beryllium hydroxide or carbonate at ordinary tern*pentturai to insure a state of supprsaturati&n of the &utph&teformer! and suddenly shaking the mass. The* %aliittnn it*elfbould contain excess of acid, and inoculation with cryMitk ofthe hexahydrate previously produced wan apparently of no as-sistance. Crystallization in the cold did not eem to cxpecitllyfavor the formation of the hexahydrate, but the one condition


to be supersaturation. Still having once produced thete it could be crystallized out of aqueous solution at

t e m p e r a t u r e s a s h ^ n as 500 and he even threw it out of solu-t a,t 90 0 by addition of boiling* alcohol. On the other hand

a t 300 the cryohydrate was reached, the hexahydratewas p r e s e n t mixed with ice. According to Levi-Malvano thel u ' x a l i y d r a t e is stable in air. The finely pulverized salt melted**t 7 & - 8 , but on removing the source of heat and cooling, theSu

' i

34 CHEMISTRY OF BERYUJUM

Beryllium TMosulphite.Factor (1901; 5) claims to have pro-duced the salt, BeS2O3 .nH2O, by the action of a solution ofsodium thiosulphate on a solution of beryllium sulphate. Someexperiments by the author lead him to believe that this is incorrectfor in his hands an admixture of these two solutions alwaysprecipitates sulphur and gives off sulphur dioxide as was to beexpected. Marignac (1875; 1) and Atterberg (1873; 7) couldnot obtain the salt.

Beryllium Dithionate.The normal salt has not been produced.Beryllium Sulphocyanate, Be(CyS)2-Hermes (1866; 2) con-

cluded that the somewhat illy defined residue obtained by theaction of the acid on beryllium carbonate was the sulphocyanate.Found it to be soluble in alcohol. Toczynski (1871; 2) wasunable to prepare the sulphocyanate with any definiteness andAtterberg (1873; 7) had no better success.

Beryllium Selenate, BeSeO44H2O.Beryllium selenate wasfirst prepared by Atterberg (1873; 7 and 8) and has been also.studied by Topsoe (1872; 1). Lt is isomorphous with the sul-phate and like the sulphate, loses water at ioo forming a di-hydrate. According to Topsoe (1872; 1) and Topsoe andChristiansen (1873; 9), it crystallizes in the rhombohedraisystem, a:b:c~i : 0.9602 10.9027, observed forms ( o n ) , (101),.(021), ( i n ) , (001). Its mean indices of refraction are

ha hb heC 1 . 4 9 9 2 1 - 4 9 7 3 1 . 4 6 3 9D 1 . 5 0 2 7 1 * 5 0 1 7 1 . 4 6 6 4F 1 . 5 1 0 1 1 . 5 0 8 4 1 - 4 7 2 5

I t s s p e c i f i c g r a v i t y ( T o p s o e ) i s 2 . 0 2 9 . R o o z e b o o m ( 1 8 9 1 ; 1 )a n d T o p s o e ( 1 8 7 2 ; 1 ) h a v e b o t h d i s c u s s e d t h e s i g n i f i c a n c e o f t h em i x e d c r y s t a l s o f t h e s u l p h a t e a n d s e l e n a t e .

B e r y l l i u m S e l e n i t e , B e S e O 3 + A q . T w o n o r m a l s e l e n i t e s findp l a c e i n l i t e r a t u r e , B e S e O 3 . H 2 O , p r e p a r e d b y A t t e r b e r g ( 1 8 7 3 ;7 ) a n d B e S e O 3 . 2 H 2 0 , p r e p a r e d b y N i l s o n ( 1 8 7 5 ; 2).N i l s o n s t a t e s t h a t h i s s a l t l o s e s o n e m o l e c u l e o f w a t e r a t

i o o . I t w a s a g u m m y m a s s d e c o m p o s a b l e b y w a t e r a n d m a d e

b y e v a p o r a t i n g t h e c o n s t i t u e n t s t o g e t h e r . F o r m u l a a r r i v e d a t

b y a n a l y s i s o f g u m m y m a s s a n d n o e v i d e n c e o f i n d i v i d u a l e x -


istence. Acid selenites (see acid salts) and so-called basicselenites (see basic salts) have been prepared in much the sameway. None of these salts should be accepted without confirma-tion.

Beryllium Tellurates and Tellurites.Berzelius (1833; 2 ) Pre~cipitated beryllium telhtrate and tellurite from solution by meansof the corresponding potassium salt. They were obtained aswhite voluminous flakes, and were probably basic mixtures butvo details are given.

Beryllium Chromite, BeCr2O4.A crystalline compound madeby Ebelmen by fusing chromic oxide, beryllium oxide and boricanhydride together and treating with hydrochloric acid. De-scribed by Mallard (1887; 4) .

Beryllium Chromate.Atterberg (1873; 7) attempted to pro-duce a neutral chromate but was not successful. The author ofthis summary and his students have repeatedly attempted toproduce a chromate of definite composition, by crystallizing fromaqueous solutions of very varied acid concentration treated withbasic carbonate, to all degrees of saturation, and evaporated bothin vacuo and in the air, but without success. If chromic acidwas present in excess it crystallized out first and no separationof another definite compound could be obtained, although it wasof course a simple matter to obtain residues containing any de-sired ratio between the beryllium and chromic acid. If car-bonate was added to saturation or even in excess of the equiva-lent amount and long before the solution was neutralized onlythe usual indefinite gurnmy basic chromates were obtained onevaporation. On the other hand Glassmann (1907; 4) claimsto have made a neutral chromate, BeCr04.HoO, by "neutraliz-ing" a chromic acid solution with basic carbonate and evaporat-ing, which he states are reddish yellow monoclinic crystals, de-composed by water.

Beryllium Molybdate, BeMoO3.2H2O.prepared by Rosen-heim and Woge (1897; 4) by boiling equivalents of molybdicacid and beryllium hydroxide suspended in water. An oily liquidlayer so obtained was separated in a separatory funnel and afterstanding two weeks in the cold of winter solidified to an aggre-


gate of needle like crystals. Analysis shows decided basicitywhich they attribute to admixture of beryllium hydroxide im-possible to remove.

Beryllium Nitrate.The normal nitrate was an article of com-merce before it found place in literature. Ordway (1858; 1,1859; 2) made a special study of the nitrates and found, as hadbeen the case with Vauqnelin (1798; 5) and Gmelin (.1801; 1)that they are extremely difficult to crystallize. By precipitatinga solution of beryllium sulphate with barium nitrate and evap-orating the solution over sulphuric acid, Ordway produced asolid mass that approached the normal nitrate in composition,but still basic as would necessarily result from any method in-volving the presence of water in quantity. Ordway shows howreadily the nitrate loses nitric anhydride and Parsons (1904; 5)has shown that by evaporating a solution of the nitrate it be-comes strongly basic below 500, and on slowly drying to 175it has become a solid which has already lost 75 per cent, of itsnitric anhydride. Atterberg (1873; 7) could make no nitrate.

The commercial crystallized nitrate, which can be obtainedalmost perfectly pure, as it is used in the incandescent mantleindustry, smells strongly of nitric anhydride, melts with verylittle heat in its own water of crystallization and immediatelybegins to show bubbles of escaping gas. On slowly increasingthe heat, the nitric anhydride is rapidly evolved leaving behinda viscous glucose like mass, which is still readily soluble inwater when it has reached the tribasic condition. Even below1750 it has become tetrabasic and loses all of its nitric anhydridebelow a red heat. The resultant oxide contains a small amountof occluded oxygen and nitrogen, which if the decomposition hasbeen gradually brought about, is equivalent to approximately0.35 cubic centimeter (Parsons, 1904; 5) of mixed gases, ofwhich approximately two-thirds are nitrogen, per gram of oxide..The nitrate is, of course, strongly acid in reaction. Accordingto Brunner (1900; 1), a solution of the nitrate of normalityN/10 to N/40 is hydrolyzed from 1.8 per cent, to 1.9 per cent.

The nitrate is easily made (1906; 13) by saturating nitric acictwith basic beryllium carbonate, evaporating to a syrupy con-

NORMAL COMPOUNDS OF BERYLLIUM Z7

sistcncy, adding strong nitric acid in excess and crystallizingtherefrom. The crystals obtained are definite in compositionand have the composition, Ite(NTOa)2.4HaO. They are highlydeliquescent, lose nitric acid readily, and are stable only inpresence of strong nitric acid or in equilibrium with its vapor.They melt in their own water of crystallization at 60.5 and aresoluble in alcohol and acetone.

Beryllium Nitrite.HeryIlium nitrite has never been prepared.The efforts of Vogcl (1903; 2) proving fruitless as the solutionimmediately hydrolyzed with loss of the oxides of nitrogen. Itmay possibly be prepared in non-aqueous solutions.

Beryllium Phosphate.---The literature of the normal phosphatesoi beryllium is very far from dear, as the few investigators whohave taken up the matter have found the material they producedof a gelatinous nature ami difficult to identify as an individualsalt. Sestini ( i8cp; 2), by boiling an acetic acid solution ofberyllium phosphate, obtained a flocculcnt precipitate to whichIn- gave the formula, \U>,( I '0 .^.31 LO-fAq. Atterberg (1873;j) obtained, by adding sodium orthophosphate to a soluble beryl-lium salt, a lloeculent precipitate to which he assigned the for-mula, \W:A V()i).J}\lJ ). Prepared by precipitating a phosphoricarid solution of beryllium hydroxide with alcohol it contained7H..O.

Beryllium Hypophosphate, 2l)eI>C)r! f 3H./).Rammolsberg-(fKoj; 4) in his studies of the hypophosphates threw down ahot solution of beryllium sulphate with sodium hypophosphaceand obtained a white precipitate having the composition, 2BePO343IKO, which on heating to 23O-25O lost one-half of itswater.

Beryllium Pyrophosphate, Hc2V./.)1.$H.Jf).~Uy precipitating asolution of srxlium pyrophosphate with a basic solution of beryl-lium nitrate, Schcffer (1859; 3) obtained a white pulverulent pre-cipitate which, on analysis, yielded results close to the theoreti-cal formula for the pyrophosphate. Atterberg (1873; 7) studiedthe reaction, but did not identify the salt.

Beryllium Phosphite and Hypophosphite.Rose (1827; 1) pre-


cipitated a solution of beryllium chloride with a solution of phos-phorus trichloride in ammonia and again (1828; 1) saturatedhypophosphorous acid with beryllium hydroxide, obtaining agummy mass1. Probably neither precipitate was the normal saltand no formula was assigned.

Beryllium Vanadate.Berzelius (1831; 3) in his researcheson the vanadates obtained a yellow, neutral, difficultly solubleberyllium vanadate which was not studied and to which no for-mula was assigned.

Beryllium Arsenate, Be3(AsO4)2.6H2O.Prepared by Atter-berg (1875; 4). Made in the same way as the correspondingphosphate which it resembled. Almost no other details.

Beryllium Antimonate, Be(SbO8)2.6H2O.This salt was pre-pared by Ebel (1887; 2) by adding a soluble beryllium salt toa hot solution of sodium metantimonate.

Beryllium Columbate.By precipitating beryllium chloride withpotassium columbate and fusing the precipitate in boric anhydrideLarsson (1896; 10) succeeded in obtaining a crystalline colum-bate containing 6.24 per cent. BeO and 89.60 per cent. Cb2O5.

Beryllium Carbonate.No normal carbonate of beryllium isknown. The carbonate, BeCO.v4H2O, claimed by Klatzo (1869;1), was a mistake and has never been made, and can not be madeunless from non-aqueous solution. The so-called basic carbon-ates are important and several double carbonates are known (seebasic salts and double carbonates).

Beryllium Silicates.The work on the normal silicates ofberyllium has been confined to the artificial production of a metasilicate, BeSiO3, phenacite, Be2SiO4, and beryl, Be,AL( Si()).Phenacite was first prepared by Ebelmen (1887; 4) by fusingtogether silicon dioxide, beryllium oxide and borax in right pro-portions. Later Hautefeuille and Perrey (1888; 4) prepared itby fusing SiO2 and BeO together using lithium vanadate andcarbonate as a mineralizing agent, and still later (1890; 14, and1893; 1) by fusing beryllium sulphate and silicic acid. Berylwas first prepared by Williams (1873; 3), by directly fusing- to-gether its constituents and later, Hautefeuille and Perrey (1888;4) prepared it by fusing together its constituents in acid lithium


molybdate. Stein (1907; 9) by fusing in a carbon tube the nec-essary quantities of BeO and SiO2 at 20000 obtained a metasilicate, BeSiOs with density 2.35 and an ortho silicate with den-sity 2.46.

Beryllium Silicotungstate.Wyrouboif (1896; 1) prepared acrystalline silicotungstate to which he gave the incomprehensibleformula, Be4(VV12SiO40)3.93H2OJ when c ystallized below 450 .Crystallized above 45 it becomes rhombohedral with 87H2O.in presence of nitric acid at 300 a 45H2O compound is obtained.

Beryllium Fluosilicate.Berzelius (1823; 1) prepared a fluo-silicate by the action of fluosilicic acid 011 beryllium hydroxide,but did not analyze or give details, and both Atterberg (1873; 7)and Marignac (1873; 1) state that it can be n r d e only in solu-tion.

Beryllium Aluminate, Be(AlO2)2.Occurs in nature as chryso-beryl (cymophane, alexandrite) and prepared artificially by Ebel-men (1851; 3) by fusing theoretical portions of alumina andberyllia in boric anhydrid and later, by Hautefeuille and Perreyby fusing a mixture of the oxides of aluminum and berylliumin leucite or nephelite.

Beryllium Perrocyanide and Perricyanide.Toczynski (1871;2) prepared beryllium ferrocyanide by adding beryllium sulphateto barium ferrocyanide as a light green mass. By oxidizingwith chlorine, he obtained the ferricyanide as an olive greenmaterial. Both were poorly denned and probably basic in natureas Atterberg (1873; 7) has pointed out.

Beryllium Nitroprusside.Toczynski (1871; 2) was not ableto prepare a nitroprusside.

Beryllium Methyl, Be(CHa)2; Beryllium Ethyl, Be(C2H5)2;Beryllium Propyl, Be(C3H7)2.Beryllium ethyl was first pre-pared by Cahours ( i860; 1) by the action of metallic berylliumen ethyl iodide in a sealed tube. In later experiments, (1873;i ) , he produced enough to study by the action of beryllium onmercury ethyl. Found it to be a colorless liquid boiling at 1850-1880. It is spontaneously combustible in air and is decomposedby water. It can be distilled in an atmosphere of carbon diox-ide. Beryllium propyl was also prepared by Cahours (1873; I )


in a similar manner by the action of beryllium on mercury pro-pyl in a sealed tube at I3O-I35. It was also a liquid boilingat 244-246 with properties similar to beryllium ethyl.

Beryllium methyl was later prepared by LavroiT (1K84; 3) ina similar manner by the action of metallic beryllium on mercurymethyl in a sealed tube at 1300. It is a white volatile crystallinesubstance decomposed by water with evolution of light, intomethane and beryllium hydroxide.

Beryllium Formate, Acetate, Propionate, Etc.Although manyattempts were made by Vauquelin (1798; 5). I'rbahi ami Lamnihe(1901 ;2,190253) and others, nouonnahnli of beryllium with anymember of the fatty acids was made until Steinmet/ ( H J O J ; 5)finally succeeded in preparing the normal acetate, !e(C\ll,,( )., )2,by heating equal parts of basic acetate, Iet( >( l\.lf...,>n, amiglacial acetic acid with five to six parts of acetic anhydride {t*r twohours in a sealed tube at 140. He obtained under the>e e*n-ditions crystals of the normal acetate, as small double refractingleaflets, which were insoluble in water, alcohol, ether, ami otherorganic solvents. They melted with decomposition at #KV" yield-ing a sublimate of the basic acetate. They were also slowly hy-drolyzed by boiling water.

Tanatar (1907; 12) claims to make the normal formate,Be(CHO2)2, by slowly evaporating" over sulphuric- arid asolution of formic acid neutralized with the ba*k carbonate,He also claims to make the basic formate, !*


acetylacetone on a solution in equivalent quantities of berylliumhydroxide in acetic acid. He found it to be a white crystal-line solid melting at 1080, easily sublimed, and boiling at 2700.Two determinations of its vapor density showed its molecularweight to correspond with the formula, Be(C5H7O2),2. Parsons(1904; 5) who used this salt as a basis in his atomic weightdeterminations made a careful study of the compound. Hefound it to be most readily prepared by the direct action ofacetylacetone on basic beryllium carbonate or hydroxide. Accord-ing to this author, the specific gravity of beryllium acetylaceton-ate is 1.168 compared to water at 40 . It is a perfectly white crys-talline substance which is slightly soluble in cold water, moresoluble in hot water and slowly hydrolyzed by boiling waterwith loss of acetylacetone and precipitation of beryllium hydrox-ide. It is readily soluble in alcohol and is easily crystallizedtherefrom in rhombic plates. It is soluble in benzene, toluene,xylene, naphtha, and all petroleum distillates, chloroform; tur-pentine, methyl alcohol, amyl alcohol, ether, ethyl acetate, ace-tone and carbon disulphide. It sublimes many degrees belowits boiling point and begins to sublime even below the boilingpoint of water. The sublimed crystals are light and flocculentwith a marked resemblance to flakes of snow. It is soluble macids setting free acetylacetone.

Beryllium Oxalate Trihydrate, BeC2O4.3H2O.Although earlyattempts were made by Vauquelin (1798; 5), Debray (1855; I )and Atterberg (1873; 7) to produce the normal oxalate, theywere not successful and it was first made by Rosenheim andWoge (1897; 4 ) . Wyrouboff (1902; 1) confirms the resultsof Rosenheim and Woge, and Parsons and Robinson (1906; 1)made a study of the system, BeO :C2O3 :H2O, also producing thenormal oxalate. All three authors produced their oxalate byadding basic beryllium carbonate or hydroxide to excess of oxalicacid and crystallizing the oxalate therefrom. It was found al-most impossible to get the salt absolutely free from excess ofoxalic acid by crystallization and to procure the perfectly neu-tral salt. Parsons and Robinson added the necessary measuredquantity of beryllium basic carbonate. Any excess of base pre-

42 CHEMISTRY 0 BERYLLIUM

vented crystallization. The crystals of the trihydrate were de-scribed by Wyrouboff (1902; 1). The crystals were figured inthe article of Parsons and Robinson and the measurements madeby Penfield and Heath (1906; 1) showed the crystals to be ortho-rhombic. The forms observed c(ooi) , d ( i o i ) , p(m). Theangles

P A P"', i n A i l l = 74i6'PAP, i n A i n = 9O6/CAP, 001 A i n = 683O'

Calculated 682o/

The first two measurements yielded the axial ratio a :b :c~0.853 : I- : I-645- No distinct cleavage was observed. The caxis is a bisectrix and the plane of the optical axis is thebrachypinacoid. In the crystal examined, the interference fig-ure was indistinct and the axial angle so large that the hyper-bolas opened out beyond the field of view.

Beryllium oxalate trihydrate is stable at room temperature.It is soluble in less than its own weight of boiling water and isbut little less soluble at ordinary temperatures. It is stronglyacid in reaction and in concentrated solution dissolves 1.85 equiv-alents of its own carbonate or hydroxide. It has a sharp sweet-ish taste. Heated at 100-1050 it loses two thirds of its waterof crystallization forming the monohydrate.

Beryllium Oxalate Monohydrate.Prepared by Rosenheim andWoge (1897; 4) , Wyrouboff (1902; 1) and by Parsons andRobinson (1906; 1). Is made by heating the trihydrate at100-1050. Heated much above this temperature it begins to losewater, at first slowly, but more rapidly as the thermometerreaches 2200, at which temperature the oxalate begins to de-compose and at 3500 is completely converted into the oxide.

Beryllium Tartrate, BeC4H4O6+3H2O.Vauquelin (1898; 5)and Toczynski (1871; 1) attempted the production of the normaltartrate, but it was first reported by Atterberg who gave to itthe formula, BeC4H4O6+3H2O. Atterberg gives few details,,but the salt is confirmed by Rosenheim and Itzig (1899; 15) whosimply state the fact. The chief characteristic of the tartratcsof beryllium and a fact which gives them especial interest is.


their abnormally great rotatory power. This fact was firstbrought out by Biot (1838; 1) on a tartrate of unstated com-position prepared by Berthier, who found the beryllium tartrateto have the largest specific rotatory power of any tartrate ex-amined, viz., in 100 millimeters +41.134 to +43.992. Rosenheimand Itzig (1899; 13) in their work on some double tartrates,(which see) confirm this fact and found the rotation of polar-ized light, both right and left, was greatly increased by the in-corporation of beryllium in the molecule. By saturating tar-taric acid with freshly precipitated beryllium hydroxide at boil-ing heat and evaporation, they obtained a basic uncrystallizableglassy mass whose analysis led to the formula, Be3C4H2O7+7H2O,which had a very high rotatory power, their four experimentsgiving [ M J ^ + 1 7 1 0 to +176.80 . The rotatory power showeda change on dilution owing to hydrolysis and the authors, wereinclined to believe they had here a beryllium salt of diberylliumtartrate, similar to potassium diberyllium tartrate, to be describedlater.

Beryllium Succinate, BeC4H4O4+2H2O.Atterberg (1893;7) obtained this salt by dissolving the hydrate or carbonatein excess of succinic acid and concentrating at a thick syrupfrom which small crystals separated. These crystals lost theirwater of crystallization at ioo. They are only stable in pres-ence of an excess of succinic acid.

Beryllium Picrate.Lea (1858; 2) reports a golden yellowcrystalline picrate made by dissolving basic beryllium carbon-ate in picric acid. No analysis, and it was probably basic.Glassmann, (1907; 6) by "neutralizing" picric acid solution withbasic beryllium carbonate obtained yellow scales which he dried inthe air and assigned the formula, Be (CflH2O7N3)2.3H2O. By wash-ing with ether, he dried it somewhat and assignedBe(C0H2O7N3)2.2H2O to the product, and since by drying atI2O-I3O he obtained a product which gave a molecular loweringin acetophenone corresponding to 465 and a BeO content nearlytheoretical, he assumed he had anhydrous Be(C6H2O7.N3)i2.He apparently measured his lowering only to- the second decimaland a slight error would have given a very different result.

44 CHICMISTKV OJ* lU'.KVI.IjrM

especially as it has been shown I 1907; ioj that diôlvin^ beryl-liuni hydroxide in solutions i its normal salt^ raises the freezingpoint, if he obtained a "neutral" solution these are the onlyconditions that could have prevailed. V he, hiniM-lf, claimsthat water (in which it was made) deeonijwjsrs the pieratr andas oxide content is no criterion of eoinjM>sihon, prt'i;i]|y withberv'llinin salts, his results need confirmation Jieitnv IKMII^ ac-cepted.

Beryllium Alpha Brom Camphor Sulphonate. !n ( \ J I H n r O .vSCX.O),, was prepared by WaMen (tXiij; 7* and allhnn^h heîves no detail of the salt itself. )w Mudiei*mui vi'llow ijry^t;tU.I*oth made by treating an aU*oh!ii- Ânn*ni n{ i\w v^rrr.pnipl-itig; acid with berylliinn arHate,

Beryllium Citraconate, l i r t ' J I / > # ; BtrylHnm Fiamaratf. Beryl-Hum Maleate, \U>VJl nr llau- J:M?M-'J*. i"? a *-ta:m tôs i^^mvexcept tile MeO content *f a --nii-futiiT !n;i*U- bv Tanrtfar M^*jr;12), by treating the r'>rrf>p**j!in^ and uith basic r^tU*tt;dr ;ui*i(*vajHir;itiii .^ There U jitliiuj IM itidirau* ib;d IIKV nt^ n,,i iiu.9usual indefinite basic miMurrs ubtuint'| iv.v-h't thrê rMj|d?t!*fiH(

C H A P T E R IV

ACID SALTS OF BERYLLIUM.Beryllium has very little tendency

Beryllium, The Chemistry and Literature Of

Documents

Transcript of Beryllium, The Chemistry and Literature Of